TW202035390A - Compound having pyrimidine ring structure and organic electroluminescent element - Google Patents

Abstract

One purpose of the present invention is to provide, as a material for organic EL elements having high efficiency and high durability, an organic compound which has excellent characteristics such as excellent electron injection/transport performance and hole blocking ability, while exhibiting high stability in a thin film state. Another purpose of the present invention is to provide an organic EL element which uses this organic compound and has high efficiency and high durability. The present invention is a compound having a pyrimidine ring structure, which is designed and chemically synthesized by focusing on the characteristics of a pyrimidine ring having electron affinity, said characteristics including excellent heat resistance and ability of having a nitrogen atom coordinated to a metal. Various prototype organic EL elements were produced using this compound, and it is found that an organic EL element according to the present invention has good element characteristics from the characteristics evaluation results of the elements.

Description

Compound with pyrimidine ring structure and organic electroluminescence element

The present invention relates to compounds and organic EL devices suitable for use in organic electroluminescence devices (hereinafter referred to as "organic EL devices") that are self-luminous devices applicable to various display devices; more specifically, it relates to having a pyrimidine ring structure The compound and the organic EL device using the compound.

Since organic EL elements are self-luminous elements, they are brighter than liquid crystal elements, have better visibility, and can provide clear displays, so they have been actively studied.

In 1987, CWTang and others of Eastman Kodak Company developed a multilayer structure element that assigns various roles to each material, and put the organic EL element using organic materials into practical use. CWTang et al. layered a phosphor that can transport electrons and an organic substance that can transport holes, and injected the charges of the two into the phosphor layer to make it emit light, thereby obtaining 1000 cd/m at a voltage below 10V. High brightness of ² or more (for example, refer to Patent Document 1 and Patent Document 2).

So far, many improvements have been made for the practical application of organic EL devices. The various roles of the multilayer structure have been further subdivided. The anode, the hole injection layer, the hole transport layer, the light emitting layer, and the The electroluminescent element of the electron transport layer, the electron injection layer, and the cathode can achieve high efficiency and durability (for example, refer to Non-Patent Document 1).

In addition, in order to further improve the luminous efficiency, it has tried to use The use of triplet excitons has been studied for phosphorescent compounds (for example, refer to Non-Patent Document 2).

In addition, they have also developed a device that utilizes the luminescence caused by thermally activated delayed fluorescence (TADF). In 2011, Kyushu University’s Anda et al. realized this by using a thermally activated delayed fluorescence material. Quantum efficiency other than 5.3% (for example, refer to Non-Patent Document 3).

The light-emitting layer is generally made by doping a fluorescent compound or a phosphorescent compound with a charge-transporting compound called a host material, or a material that emits delayed fluorescence. As described in the above non-patent literature, the selection of organic materials in the organic EL device will greatly affect the efficiency and durability of the device (for example, refer to Non-Patent Literature 2).

In an organic EL device, the charges injected by the two electrodes are recombined in the light-emitting layer to obtain light. However, what is important is how to efficiently transfer the two charges of holes and electrons to the light-emitting layer. Therefore, by improving the electron injection and mobility, the probability of recombination of holes and electrons in the light-emitting layer is increased, and the holes transported from the anode side are enclosed in the light-emitting layer to prevent the electron transport layer. Deterioration or sealing of excitons generated in the light-emitting layer to create an environment that is easier to recombine, thereby obtaining high-efficiency light. Therefore, the role of electron transport materials is important, and electron transport materials with high electron injection, high electron mobility, high hole blocking properties, and high durability against holes are required.

In addition, regarding the life of the device, the heat resistance or amorphousness of the material is also important. Materials with low heat resistance are due to the heat generated when the device is driven. Even low temperatures can cause thermal decomposition and deterioration of the material. A material with low amorphousness will crystallize the thin film even in a short time, and the device will deteriorate. Therefore, the materials used require high heat resistance, Good crystallinity.

A typical luminescent material, ginseng (8-quinolinolato) aluminum (hereinafter referred to as Alq3) is generally used as an electron transport material, but its electron movement is slow and its work function is 5.6 eV, so it cannot be said that the hole blocking performance is sufficient.

As a compound with improved characteristics such as electron injection and mobility, a compound having a benzotriazole structure has been proposed (for example, Patent Document 3). However, in terms of using these compounds in an electron transport layer element, luminous efficiency, etc. Although the improvement is still insufficient, further lower driving voltage or higher luminous efficiency is still required.

In addition, as an electron transport material with excellent hole blocking properties, 3-(4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-tri Azole (hereinafter referred to as TAZ) (for example, refer to Patent Document 4).

Since TAZ has a high work function of 6.6 eV and high hole blocking ability, it is used as an electron transporting layer laminated on the cathode side in a fluorescent light-emitting layer or a phosphorescent light-emitting layer produced by vacuum evaporation or coating. The hole blocking layer contributes to the improvement of the efficiency of the organic EL device (for example, refer to Non-Patent Document 4).

However, TAZ has a major problem of low electron transport properties, and needs to be combined with electron transport materials with high electron transport properties to produce organic EL devices (for example, refer to Non-Patent Document 5).

Furthermore, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), which is known as an electron transport material, has a work function of as high as 6.7 eV and high hole blocking ability, but due to The glass transition point (Tg) is as low as 83°C, so the film lacks stability, and it is hard to say that it can fully function as a hole blocking layer.

Any material has insufficient membrane stability or insufficient function of preventing holes. In order to improve the device characteristics of organic EL devices, an injection of electrons, An organic compound with excellent transport performance and hole blocking ability and high stability in the film state.

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: United States Patent US5792557

Patent Document 2: US Patent US5639914

Patent Document 3: US Patent US9123897

Patent Document 4: US Patent US5869199

Patent Document 5: US Patent US2017/186967

Patent Document 6: US Patent US9199966

Patent Document 7: European Patent EP2684932

Patent Document 8: US Patent US6878469

Patent Document 9: US Patent US8470454

Patent Document 10: US Patent US2017/186967

[Non-Patent Literature]

Non-Patent Document 1: The 9th Workshop of the Society of Applied Physics, 55~61 pages (2001)

Non-Patent Document 2: Preliminary Collection of the 9th Seminar of the Applied Physics Society, 23~31 pages (2001)

Non-Patent Document 3: Appl. Phys. Let., 98, 083302 (2011)

Non-Patent Document 4: The 50th Joint Lecture on Applied Physics, 28p-A-6, 1413 pages (2003)

Non-Patent Document 5: The Journal of the Organic Molecules and Bioelectronics Sub-committee of the Applied Physics Society, Volume 11, Number 1, Pages 13-19 (2000)

Non-Patent Document 6: J. Org. Chem. 2001, 66, 7125-7128

The purpose of the present invention is to provide an organic compound with superior characteristics that can be used as a high-efficiency and high-durability organic EL device material, has excellent electron injection and transport properties, has hole blocking ability, and has high stability in a thin film state; Furthermore, an organic EL element with high efficiency and high durability using this compound is provided.

As the physical properties of the organic compound to be provided by the present invention, for example: (1) good electron injection characteristics, (2) high mobility of electrons, (3) excellent hole blocking ability, (4) Stable film state, (5) Excellent heat resistance. In addition, as the physical characteristics of the organic EL device to be provided by the present invention, for example: (1) high luminous efficiency and power efficiency, (2) low light-emitting initial voltage, (3) low practical driving voltage, ( 4) Long life.

Therefore, in order to achieve the above-mentioned object, the inventors of the present case focused on the electron affinity of the nitrogen atom in the pyrimidine ring, which has the ability to coordinate with the metal and is excellent in heat resistance. They designed a compound with a pyrimidine ring structure and chemically synthesized it. The compound was tested as various organic EL devices, and the characteristics of the device were evaluated. As a result, the present invention was completed.

1) That is, the present invention is a compound having a pyrimidine ring structure represented by the following general formula (a-1);

[化1]

(In the formula, A and B may be the same or different from each other, and represent the following structural formula (b-1), Ar represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted Substituted condensed polycyclic aromatic group. R represents hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, A substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a linear or branched alkyl group with 1 to 6 carbon atoms that may have a substituent, and may also have Cycloalkyl groups with 5-10 carbon atoms as substituents, linear or branched alkenyl groups with 2-6 carbon atoms that may have substituents, and 1-6 carbon atoms that may also have substituents The straight-chain or branched alkyloxy group, or the cycloalkyloxy group with 5-10 carbon atoms which may also have substituents;)

[化2] ----L──Het (b-1)

基、取代或未取代之喹啉基、取代或未取代之異喹啉基、取代或未取代之啡啉基、取代或未取代之吲哚基、取代或 未取代之氮雜茀基、取代或未取代之二氮雜茀基、取代或未取代之氮雜螺二茀基、或取代或未取代之二氮雜螺二茀基，虛線表示與嘧啶環間之鍵結部位。) (In the formula, L represents a single bond, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted divalent group of a condensed polycyclic aromatic group; Het represents a substituted or Unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted three

Group, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted indolyl, substituted or unsubstituted azepinyl, substituted Or unsubstituted diazaspirodiazepine group, substituted or unsubstituted azaspirodiazepine group, or substituted or unsubstituted diazaspirodiazepine group, the dotted line indicates the bonding site with the pyrimidine ring. )

2) In addition, the present invention is a compound having a pyrimidine ring structure described in 1) above, and is represented by the following general formula (a-2);

[化3]

(In the formula, A, B, Ar and R have the same meaning as the above general formula (a-1).)

3) In addition, the present invention is a compound having a pyrimidine ring structure described in 1) above, which is represented by the following general formula (a-3);

[化4]

(In the formula, A, B, Ar and R have the same meaning as the above general formula (a-1).)

4) In addition, the present invention is a compound having a pyrimidine ring structure described in 2) above, and the above A and B are different from each other.

5) In addition, the present invention is a chemical compound having a pyrimidine ring structure described in 3) above The above-mentioned A and B are different from each other.

6) In addition, the present invention is a compound having a pyrimidine ring structure as described in 4) above. In the above structural formula (b-1), L represents a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group , Substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, or substituted or unsubstituted biphenyl.

7) In addition, the present invention is a compound having a pyrimidine ring structure as described in 5) above. In the above structural formula (b-1), L represents a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group , Substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, or substituted or unsubstituted biphenyl.

8) In addition, the present invention is a compound having a pyrimidine ring structure described in 6) above, and Het in the above structural formula (b-1) represents an unsubstituted pyridyl group, an unsubstituted quinolinyl group, and an unsubstituted isoquinoline Linyl, or unsubstituted phenanthroline.

9) In addition, the present invention is a compound having a pyrimidine ring structure as described in 7) above. The Het in the above structural formula (b-1) represents an unsubstituted pyridyl group, an unsubstituted quinolinyl group, and an unsubstituted isoquinoline Linyl, or unsubstituted phenanthroline.

10) In addition, the present invention is an organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween; it is characterized in that any one of 1) to 9) has a pyrimidine The compound of the ring structure is used as a constituent material of at least one organic layer.

11) In addition, the present invention is the organic EL device described in 10), wherein the organic layer using the compound having a pyrimidine ring structure is an electron transport layer.

12) In addition, the present invention is the organic EL device described in 10), wherein the organic layer using a compound having a pyrimidine ring structure is a hole blocking layer.

13). Furthermore, the present invention is the organic EL device described in 10) above, which is The above-mentioned organic layer using a compound having a pyrimidine ring structure is a light-emitting layer.

14) In addition, the present invention is the organic EL device described in 10), wherein the organic layer using the compound having a pyrimidine ring structure is an electron injection layer.

1: glass substrate

2: Transparent anode

3: hole injection layer

4: Electric hole transport layer

5: Light-emitting layer

6: Hole blocking layer

7: Electron transport layer

8: Electron injection layer

9: Cathode

Fig. 1 is a diagram showing the configuration of organic EL devices of Examples 17 to 30 and Comparative Examples 1 to 4.

The compound having a pyrimidine ring structure of the present invention is a compound represented by the following general formula (a-1).

[化5]

(In the formula, A and B may be the same or different from each other, and represent the following structural formula (b-1), Ar represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted Substituted condensed polycyclic aromatic group. R represents hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, A substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a linear or branched alkyl group with 1 to 6 carbon atoms that may have a substituent, and may also have Cycloalkyl groups with 5-10 carbon atoms as substituents, linear or branched alkenyl groups with 2-6 carbon atoms that may have substituents, and 1-6 carbon atoms that may also have substituents The linear or branched alkyloxy group, or can also have Substituted cycloalkyloxy group with 5 to 10 carbon atoms;)

[化6] ----L──Het (b-1)

基、取代或未取代之喹啉基、取代或未取代之異喹啉基、取代或未取代之啡啉基、取代或未取代之吲哚基、取代或未取代之氮雜茀基、取代或未取代之二氮雜茀基、取代或未取代之氮雜螺二茀基、或取代或未取代之二氮雜螺二茀基，虛線表示與嘧啶環間之鍵結部位。) (In the formula, L represents a single bond, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted divalent group of a condensed polycyclic aromatic group; Het represents a substituted or Unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted three

Group, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted indolyl, substituted or unsubstituted azepinyl, substituted Or unsubstituted diazaspirodiazepine group, substituted or unsubstituted azaspirodiazepine group, or substituted or unsubstituted diazaspirodiazepine group, the dotted line indicates the bonding site with the pyrimidine ring. )

基、呋喃基、吡咯基、噻吩基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并

唑基、苯并噻唑基、氮雜茀基、二氮雜茀基、氮雜螺二茀基、二氮雜螺二茀基、喹

啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、萘啶基、啡啉基、吖啶基、及咔啉基等，尚有由碳數6~30所構成之芳基、及由碳數2~20所構成之雜芳 基等。 In the above general formula (a-1), "substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group" and "substituted or unsubstituted condensed polycyclic aromatic group" represented by Ar and R "Aromatic hydrocarbon group", "aromatic heterocyclic group" and "condensed polycyclic aromatic group" in "group", specific examples include: phenyl, biphenyl, triphenyl, naphthyl, anthracenyl, phenanthrene Group, stilbene, spirodiphenyl, indenyl, pyrenyl, perylene, propylene(di)ene pyrenyl, triphenylene, pyridyl, pyrimidinyl, triacrine

Group, furyl, pyrrolyl, thienyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzo

Azolyl, benzothiazolyl, azapyridine, diazapyridinium, azaspirodipyridinium, diazaspirodipyridinium, quine

Alrinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, naphthyridinyl, phenanthroline, acridinyl, and carboline group, etc., with carbon numbers 6~30 The formed aryl group, and the heteroaryl group composed of 2-20 carbons, etc.

唑基、苯并噻唑基、喹

啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、咔啉基等芳香族雜環基。此等取代基亦可進一步由上述例示取代基所取代。又，經此等取代基所取代之苯環、或於同一苯環上經複數取代之取代基彼此，亦可經由單鍵、取代或未取代之亞甲基、氧原子或硫原子而彼此鍵結形成環。 The "substituent" in the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" and "substituted condensed polycyclic aromatic group" represented by Ar and R in the above general formula (a-1) can be specifically For example: deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; silyl group such as trimethylsilyl group and triphenylsilyl group; methyl group, ethyl group, propyl group Linear or branched alkyl with 1 to 6 carbon atoms; methoxy, ethoxy, propoxy and other linear or branched alkyloxy with 1 to 6 carbon atoms ; Alkenyl such as vinyl and allyl; aryloxy such as phenoxy and tolyloxy; arylalkyloxy such as benzyloxy and phenethoxy; phenyl, biphenyl, triphenyl, Aromatic hydrocarbon groups such as naphthyl, anthracenyl, phenanthryl, stilbyl, spirodiphenyl, indenyl, pyrenyl, perylene, propenyl, triphenylene and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups ; Pyridyl, thienyl, furanyl, pyrrolyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzo

Azolyl, benzothiazolyl, quine

Aromatic heterocyclic groups such as olinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carbolinyl. These substituents may be further substituted with the above-exemplified substituents. In addition, the benzene ring substituted by these substituents, or the plural substituted substituents on the same benzene ring, may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom The knot forms a ring.

In the above general formula (a-1), the "linear or branched alkyl group with 1 to 6 carbon atoms which may have substituents" represented by R in the above general formula (a-1), "the number of carbon atoms which may also have substituents "5-10 cycloalkyl" and "linear or branched alkyl with 1 to 6 carbon atoms", "linear or branched alkyl with 1 to 6 carbon atoms", "Cycloalkyl with 5 to 10 carbon atoms" and "Straight-chain or branched alkenyl with 2 to 6 carbon atoms", specific examples include methyl, ethyl, n-propyl, isopropyl , N-butyl, isobutyl, tertiary butyl, N-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, vinyl, allyl, isopropenyl, and 2-butene Base etc. The benzene ring substituted by these substituents, or the plural substituted substituents on the same benzene ring, can also be through a single bond, substituted or unsubstituted methylene, substituted or unsubstituted amine group, and oxygen atom Or sulfur atoms are bonded to each other to form a ring.

In the above general formula (a-1), the "linear or branched alkyl group with 1 to 6 carbon atoms which may have substituents" represented by R in the above general formula (a-1), "the number of carbon atoms which may also have substituents The "substituent" in the "5-10 cycloalkyl group" and "the linear or branched alkenyl group with 2-6 carbon atoms that may have substituents", specifically, for example, the general formula (a -1) In the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" and "substituted condensed polycyclic aromatic group" in the "substituted aromatic hydrocarbon group", "substituted condensed polycyclic aromatic group" in -1), the same examples, all aspects For example, the same ones may also be mentioned.

In the above general formula (a-1), the "linear or branched alkyloxy group having 1 to 6 carbon atoms which may also have substituents" and "the carbon which may have substituents "Cycloalkyloxy group with 5 to 10 atoms" in "Linear or branched alkyloxy group with 1 to 6 carbon atoms" and "Cycloalkyloxy group with 5 to 10 carbon atoms" Specific examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tertiary butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, ring Hexyloxy, cycloheptyloxy, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy and the like. The benzene ring substituted by these substituents, or the plural substituted substituents on the same benzene ring, can also be through a single bond, substituted or unsubstituted methylene, substituted or unsubstituted amine group, and oxygen atom Or sulfur atoms are bonded to each other to form a ring.

In the above general formula (a-1), the "linear or branched alkyloxy group having 1 to 6 carbon atoms which may also have substituents" and "the alkyloxy group which may have substituents Specific examples of the "substituent" in the "cycloalkyloxy group having 5 to 10 carbon atoms" include the "substituted aromatic hydrocarbon group" and "substituted aromatic hydrocarbon group" represented by Ar and R in the general formula (a-1). The "substituent" in the "group heterocyclic group" and "substituted condensed polycyclic aromatic group" is the same as exemplified, and all aspects can be, for example, the same.

The "substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group" and "substituted or unsubstituted condensed polycyclic aromatic group" represented by L in the above structural formula (b-1) "Aromatic hydrocarbon group", "aromatic heterocyclic group" and "condensed polycyclic aromatic group" in ", for example, "substituted or unsubstituted" represented by Ar and R in general formula (a-1) "Aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group" and "substituted or unsubstituted condensed polycyclic aromatic group" in the "aromatic hydrocarbon group", "aromatic heterocyclic group" and "condensation The "polycyclic aromatic group" exemplifies a divalent group in which one hydrogen atom is removed, and all aspects may be, for example, the same.

The "substituent" in the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group", and "substituted condensed polycyclic aromatic group" represented by L in the above structural formula (b-1), specifically, for example The same as the examples of the "substituent" in the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" and "substituted condensed polycyclic aromatic group" represented by Ar and R in general formula (a-1) In addition, all aspects may be the same, for example.

基」、「取代喹啉基」、「取代異喹啉基」、「取代啡啉基」、「取代吲哚基」、「取代氮雜茀基」、「取代二氮雜茀基」、「取代氮雜螺二茀基」及「取代二氮雜螺二茀基」中之「取代基」，具體可舉例如與一般式(a-1)中的Ar、R所示之「取代芳香族烴基」、「取代芳香族雜環基」及「取代縮合多環芳香族基」中之「取代基」所例示相同者，所有態樣亦可舉例如相同者。 The "substituted pyridyl", "substituted pyrimidinyl", "substituted three" represented by Het in the above structural formula (b-1)

"Group", "Substituted quinolinyl", "Substituted isoquinolinyl", "Substituted phenanthryl", "Substituted indolyl", "Substituted azepinyl", "Substituted diazepinyl", " The "substituents" in "substituted azaspirodisyl" and "substituted diazaspirodisyl" can be specifically exemplified with the "substituted aromatics" represented by Ar and R in general formula (a-1) The examples of the "substituent" in the "hydrocarbon group", "substituted aromatic heterocyclic group" and "substituted condensed polycyclic aromatic group" are the same, and all aspects may be, for example, the same.

In the present invention, from the viewpoints of electron injection, transport performance, hole blocking ability, and stability in a thin film state, Ar in the above general formula (a-1) is preferably a substituted or unsubstituted aromatic hydrocarbon group, Or substituted or unsubstituted condensed polycyclic aromatic group, more preferably substituted or unsubstituted phenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted phenanthrenyl Or substituted or unsubstituted spirodiphenyl.

Moreover, R is preferably a hydrogen atom.

In the present invention, from the viewpoints of electron injection, transport performance, hole blocking ability, and stability in a thin film state, the above structural formula (b-1) L is preferably a single bond, substituted or unsubstituted phenylene , Substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, or substituted or unsubstituted biphenyl, preferably unsubstituted phenylene.

In addition, Het is preferably an unsubstituted pyridyl group, an unsubstituted quinolyl group or an unsubstituted isoquinolyl group.

From the viewpoints of electron injection, transport performance, hole blocking ability, and stability in a thin film state, the compound having a pyrimidine ring structure of the present invention is preferably the following general formula (a-2) or the following general formula ( a-3) The compound shown.

[化7]

(In the formula, A, B, Ar and R have the same meaning as the above general formula (a-1).)

[化8]

(In the formula, A, B, Ar and R have the same meaning as the above general formula (a-1).)

From the viewpoints of electron injection, transport performance, hole blocking ability, and stability in a thin film state, the compound having a pyrimidine ring structure of the present invention is preferably one represented by the above general formula (a-2).

That is, the compound with a pyrimidine ring structure of the present invention is preferably represented by the above general formula (a-2), where Ar is substituted or unsubstituted phenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted Phenanthrene group, substituted or unsubstituted quinolyl or substituted or unsubstituted spirodipyryl, R is hydrogen atom, L is unsubstituted phenyl, Het is unsubstituted pyridyl, unsubstituted quinolinyl or unsubstituted Substituted isoquinolinyl.

The compound with the pyrimidine ring structure of the present invention has the following characteristics: (1) good electron injection characteristics, (2) large electron mobility, (3) excellent hole blocking ability, (4) stable existence in a thin film state , (5) Excellent heat resistance. In addition, the organic EL device of the present invention has the following characteristics: (1) high luminous efficiency and power efficiency, (2) low light-emitting initial voltage, (3) low practical driving voltage, and (4) long life.

The compound with the pyrimidine ring structure of the present invention has good electron injection characteristics and high electron mobility. Thereby, an organic EL element having an electron injection layer and/or an electron transport layer made of the compound as an electron injection material and/or electron transport material improves the electron transport efficiency of the light emitting layer and the luminous efficiency is improved, while The driving voltage is reduced and the durability is improved.

The compound with the pyrimidine ring structure of the present invention has excellent hole blocking ability and electron transport properties, and is also stable in a thin film state, and has the characteristics of being enclosed in excitons generated in the light-emitting layer. As a result, the organic EL device with a hole blocking layer manufactured using the compound as a hole blocking material has an increased probability of recombination of holes and electrons to suppress thermal deactivation, so it has high luminous efficiency and reduced driving voltage As the current resistance is improved, the maximum luminous brightness is increased.

The compound having a pyrimidine ring structure of the present invention has excellent electron transport properties and a wide energy gap. Thereby, an organic EL device having a light-emitting layer manufactured using the compound as a host material forms a light-emitting layer by supporting a fluorescent light-emitting body, a phosphorescent light-emitting body, and a delayed fluorescent light-emitting body of so-called dopants , And reduce the driving voltage and improve the luminous efficiency.

Therefore, the compound having a pyrimidine ring structure of the present invention can be used as a material for the electron injection layer, electron transport layer, hole blocking layer or light-emitting layer of organic EL devices, and can improve the luminous efficiency and driving voltage of conventional organic EL devices. And durability.

The compounds having a pyrimidine ring structure of the present invention are novel compounds, but these compounds can be synthesized according to methods known per se (for example, refer to Patent Document 5 and Non-Patent Document 6).

The purification of the compound with the pyrimidine ring structure of the present invention can be carried out by the following: purification by column chromatography; purification by adsorption of silica gel, activated carbon, activated clay, etc.; recrystallization or crystallization by solvent Method; sublimation refining method, etc.

Among the compounds having a pyrimidine ring structure represented by the general formula (a-1) of the present invention, specific examples of preferred compounds are shown below, but the present invention is not limited to these compounds.

[化9]

[化10]

[化11]

[化12]

[化13]

[化14]

[化15]

[化16]

[化17]

The compound having a pyrimidine ring structure of the present invention can be used as a constituent material of the light-emitting layer, electron injection layer, electron transport layer, and hole blocking layer of an organic EL device. In particular, since the mobility of electrons is high, it is a compound suitable as a constituent material of the electron injection layer or the electron transport layer.

The organic EL device of the present invention has a pair of electrodes and at least one organic layer sandwiched between them, and is characterized by using the compound having a pyrimidine ring structure of the present invention as a constituent material of the at least one organic layer. Examples of the organic layer include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The compound having a pyrimidine ring structure of the present invention can be suitably used As a constituent material of the light-emitting layer, hole blocking layer, electron transport layer, and electron injection layer.

As the structure of the organic EL device of the present invention, for example, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially provided on a substrate; Those with an electron blocking layer between the transport layer and the light-emitting layer; those with a hole blocking layer between the light-emitting layer and the electron transport layer. In these multi-layer structures, several layers such as organic layers can be omitted, or, for example, it can be used as a single layer of a hole injection layer and a hole transport layer, or a layer of an electron injection layer and an electron transport layer. The composition and so on. In addition, it can be used as a stack of two or more organic layers with the same function. It can also be used as a stack of two hole transport layers, two stacks of light-emitting layers, and two stacks of electron transport layers. The composition and so on.

As the anode of the organic EL device of the present invention, ITO or an electrode material with a large work function like gold can be used. As the hole injection layer of the organic EL device of the present invention, a porphyrin compound represented by copper phthalocyanine, a starburst type triphenylamine derivative, a triphenylamine structure having two or more in the molecule, or Carbazolyl structure and arylamine compounds connected by single bonds or divalent groups without heteroatoms, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coatings Cloth-type polymer materials, etc. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

As the hole transport layer of the organic EL device of the present invention, N,N'-diphenyl-N,N'-bis(m-tolyl)-benzidine (hereinafter referred to as TPD) or N,N'- Diphenyl-N,N'-bis(α-naphthyl)-benzidine (hereinafter referred to as NPD), N,N,N',N'-tetraphenylbenzidine and other benzidine derivatives, 1, 1-bis[(Di-4-tolylamino)phenyl]cyclohexane (hereinafter referred to as TAPC), and having two or more triphenylamine structures or carbazolyl structures in the molecule and each with Single bond or arylamine compound of a structure connected by a divalent group not containing a heteroatom, etc. These can be formed into a film alone, or mixed with other materials to form a single layer, or can be used as a layered structure in which the above-mentioned plural materials are separately formed into films, and the above-mentioned plural materials are mixed and formed into a film. A layered structure in which layers are stacked on top of each other, or a layer in which the above-mentioned plural materials are separately formed into a film and a layer in which a film is formed by mixing them. In addition, as the hole injection and transport layer, poly(3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT)/poly(styrene sulfonic acid) (hereinafter referred to as PSS) and other coating types can be used. Molecular materials. These materials can use evaporation, spin coating or inkjet The thin film is formed by well-known methods.

In addition, as the hole injection layer or the hole transport layer, it is possible to use: a material commonly used for this layer is further P-doped with tribromoaniline hexachloroantimony or an axene derivative (for example, refer to Patent Document 7); And a part of the structure has a polymer compound such as TPD and other benzidine derivatives.

As the electron blocking layer of the organic EL device of the present invention, 4,4',4"-tris(N-carbazolyl)triphenylamine (hereinafter referred to as TCTA), 9,9-bis[4- (Carbazol-9-yl)phenyl) pyrene, 1,3-bis(carbazol-9-yl)benzene (hereinafter referred to as mCP), 2,2-bis(4-carbazol-9-ylphenyl) ) Carbazole derivatives such as adamantane (hereinafter referred to as Ad-Cz), with 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl] -9H-茀 is represented by compounds with triphenylsilyl and triarylamine structures and other compounds with electron blocking effect. These can be formed into films alone or mixed with other materials to form a single layer, or It can also be made into a layered structure in which layers of the above-mentioned plural materials are separately formed into films, a layered structure in which layers of the above-mentioned plural materials are mixed and formed into films are stacked on each other, or a layer in which the above-mentioned plural materials are separately formed into films and mixed together A layered structure in which the film-forming layers are stacked. These materials can be formed into thin films using well-known methods such as vapor deposition, spin coating, or inkjet methods.

唑衍生物、聚對伸苯基伸乙烯基衍生物等。又，發光層可由主體材料與摻雜劑材料構成，較佳使用蒽衍生物作為主體材料，但除了以本發明之具有嘧啶環構造之化合物為首的上述發光材料之外，亦可使用具有吲哚環作為縮合環之部分構造之雜環化 合物、具有咔唑環作為縮合環之部分構造之雜環化合物、咔唑衍生物、噻唑衍生物、苯并咪唑衍生物、聚二烷基茀衍生物等。又，作為摻雜劑材料，可使用喹吖酮、香豆素、紅螢烯、苝及此等之衍生物、苯并吡喃衍生物、若丹明衍生物、胺基苯乙烯基衍生物等。此等可單獨成膜，亦可與其它材料混合而成膜為單層，或亦可作成為將上述複數材料分別單獨成膜之層彼此積層的積層構造、將上述複數材料混合並成膜之層彼此積層的積層構造、或將上述複數材料分別單獨成膜之層及混合而成膜之層進行積層的積層構造。此等材料可使用蒸鍍法、旋塗法或噴墨法等公知方法進行薄膜形成。 As the light-emitting layer of the organic EL device of the present invention, in addition to the compound having a pyrimidine ring structure of the present invention, metal complexes of quinolinol derivatives such as Alq ₃ , and various metal complexes, anthracene Derivatives, bisstyrylbenzene derivatives, pyrene derivatives,

Azole derivatives, polyparaphenylene vinylene derivatives, etc. In addition, the light-emitting layer may be composed of a host material and a dopant material. Anthracene derivatives are preferably used as the host material. However, in addition to the above-mentioned light-emitting materials including the compound having a pyrimidine ring structure of the present invention, an indole Heterocyclic compounds with a ring as a part of the condensed ring, heterocyclic compounds with a carbazole ring as a part of the condensed ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, polydialkyl phosphonium derivatives, etc. . In addition, as dopant materials, quinacridone, coumarin, fluorene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives can be used Wait. These can be formed into a film alone, or mixed with other materials to form a single layer, or can be used as a layered structure in which the above-mentioned plural materials are separately formed into films, and the above-mentioned plural materials are mixed and formed into a film. A layered structure in which layers are stacked on top of each other, or a layer in which the above-mentioned plural materials are separately formed into a film and a layer in which a film is formed by mixing them. These materials can be formed into thin films using well-known methods such as vapor deposition, spin coating, or inkjet methods.

Furthermore, phosphorescent emitters can also be used as luminescent materials. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Green phosphorescent emitters such as Ir(ppy) ₃ , blue phosphorescent emitters such as FIrpic and FIr6, red phosphorescent emitters such as Btp ₂ Ir(acac), etc. are used. As the host material at this time, the host material for hole injection and transport can use 4,4'-bis(N-carbazolyl)biphenyl (hereinafter referred to as CBP), TCTA, mCP and other carbazole derivatives. , The compound with pyrimidine ring structure of the present invention can still be used. In addition, as a host material for electron transport properties, p-bis(triphenylsilyl)benzene (hereinafter referred to as UGH2) or 2,2',2"-(1,3,5-phenylene)-reference can be used (1-Phenyl-1H-benzimidazole) (hereinafter referred to as TPBI), etc., can produce high-performance organic EL devices.

The doping of the phosphorescent light-emitting material to the host material is to avoid concentration quenching, and is preferably performed by co-evaporation in a range of 1 to 30% by weight relative to the entire light-emitting layer.

In addition, as the luminescent material, CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, 4CzIPN, etc. can also be used to emit delayed fluorescence (e.g. For example, refer to Non-Patent Document 3). These materials can be formed into thin films using well-known methods such as vapor deposition, spin coating, or inkjet methods.

唑衍生物、三唑衍生物、三

衍生物等具有電洞阻止作用的化合物。此等材料亦可兼為電子輸送層之材料。此等可單獨成膜，亦可與其它材料混合而成膜為單層，或亦可作成為將上述複數材料分別單獨成膜之層彼此積層的積層構造、將上述複數材料混合並成膜之層彼此積層的積層構造、或將上述複數材料分別單獨成膜之層及混合而成膜之層進行積層的積層構造。此等材料可使用蒸鍍法、旋塗法或噴墨法等公知方法進行薄膜形成。 As the hole blocking layer of the organic EL device of the present invention, in addition to the compound having a pyrimidine ring structure of the present invention, phenanthroline derivatives such as Yutongling (hereinafter referred to as BCP) and quinolinol derivatives such as BAlq can be used. Metal complexes, various rare earth complexes,

Azole derivatives, triazole derivatives, three

Derivatives and other compounds with hole blocking effect. These materials can also serve as materials for the electron transport layer. These can be formed into a film alone, or mixed with other materials to form a single layer, or can be used as a layered structure in which the above-mentioned plural materials are separately formed into films, and the above-mentioned plural materials are mixed and formed into a film. A layered structure in which layers are stacked on top of each other, or a layer in which the above-mentioned plural materials are separately formed into a film and a layer in which a film is formed by mixing them. These materials can be formed into thin films using well-known methods such as vapor deposition, spin coating, or inkjet methods.

衍生物、

二唑衍生物、吡啶衍生物、苯并咪唑衍生物、噻二唑衍生物、蒽衍生物、碳化二亞胺衍生物、喹

啉衍生物、吡啶并吲哚衍生物、啡啉衍生物、矽咯衍生物等。此等可單獨成膜，亦可與其它材料混合而成膜為單層，或亦可作成為將上述複數材料分別單獨成膜之層彼此積層的積層構造、將上述複數材料混合並成膜之層彼此積層的積層構造、或將上述複數材料分別單獨成膜之層及混合而成膜之層進行積層的積層構造。此等材料可使用蒸鍍法、旋塗法或噴墨法等公知方法進行薄膜形成。 As the electron transport layer of the organic EL device of the present invention, in addition to the compound having a pyrimidine ring structure of the present invention, metal complexes of quinolinol derivatives such as Alq ₃ and BAlq, and various metal complexes can be used , Triazole derivatives, three

derivative,

Diazole derivatives, pyridine derivatives, benzimidazole derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quine

Phytoline derivatives, pyridoindole derivatives, phenanthroline derivatives, silica derivatives, etc. These can be formed into a film alone, or mixed with other materials to form a single layer, or can be used as a layered structure in which the above-mentioned plural materials are separately formed into films, and the above-mentioned plural materials are mixed and formed into a film. A layered structure in which layers are stacked on top of each other, or a layer in which the above-mentioned plural materials are separately formed into a film and a layer in which a film is formed by mixing them. These materials can be formed into thin films using well-known methods such as vapor deposition, spin coating, or inkjet methods.

As the electron injection layer of the organic EL element of the present invention, in addition to the present invention In addition to compounds with a pyrimidine ring structure, metal complexes of alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride, and quinolinol derivatives such as lithium quinolol can be used. Metal oxides such as aluminum, or metals such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), cesium (Cs), etc., but among the better choices of electron transport layer and cathode, The electron injection layer is omitted.

Furthermore, in the electron injection layer or the electron transport layer, a material generally used for this layer may be further N-doped with metals such as cesium.

As the cathode of the organic EL device of the present invention, an electrode material with a low work function like aluminum, or an alloy with a lower work function like magnesium-silver alloy, magnesium indium alloy, and aluminum-magnesium alloy can be used as the electrode material.

Since the organic EL element of the present invention uses the compound having a pyrimidine ring structure of the present invention, which is superior in electron injection and transport performance, film stability, or durability, as a constituent material, it can be improved compared to conventional organic EL elements. The electron transport efficiency of the electron transport layer to the light-emitting layer improves the luminous efficiency, and at the same time can reduce the driving voltage and improve the durability, and can achieve high efficiency, low driving voltage and long life.

[Example]

Hereinafter, the embodiments of the present invention will be described in detail with examples, but the present invention is mentioned without departing from the gist and is not limited to the following examples.

[Example 1]

<Synthesis of 2-{4-(phenanthrene-9-yl)-phenyl}-4,6-bis-{4-(pyridin-3-yl)-phenyl}-pyrimidine (compound-5)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入H₂O，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結晶精製，獲得2-{4-(菲-9-基)-苯基}-4,6-雙-{4-(吡啶-3-基)-苯基}-嘧啶(化合物-5)之白色粉體：7.9g(產率62%)。 Fill the reaction vessel with 4,6-bis-(4-chloro-phenyl)-2-{4-(phenanthrene-9-yl)-phenyl}-pyrimidine: 11.0g, 3-pyridylboronic acid: 5.9 g. Ginseng (dibenzylideneacetone)dipalladium (0): 0.9g, tricyclohexylphosphine: 1.1g, potassium carbonate: 8.2g, in 1,4-di

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, H ₂ O was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and purified with a monochlorobenzene solvent to obtain 2-{4-(phenanthrene-9-yl)-phenyl}-4,6-bis-{4-(pyridin-3-yl) -Phenyl}-pyrimidine (compound-5) white powder: 7.9g (62% yield).

[化18]

The structure of the obtained white powder was identified by NMR.

The following 30 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.00(2H), 8.93(2H), 8.84(1H), 8.78(1H), 8.69(2H), 8.51(4H), 8.18(1H), 8.08-7.94(4H), 7.88-7.55 (11H), 7.47(1H), 7.45(1H)

[Example 2]

<Synthesis of 2-(10-phenyl-anthracene-9-yl)-4,6-bis-{4-(pyridin-3-yl)-phenyl}-pyrimidine (compound-12)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入H₂O，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結 晶精製，獲得2-(10-苯基-蒽-9-基)-4,6-雙-{4-(吡啶-3-基)-苯基}-嘧啶(化合物-12)之白色粉體：1.5g(產率25%)。 Fill the reaction vessel with 4,6-bis-(4-chloro-phenyl)-2-(10-phenyl-anthracene-9-yl)-pyrimidine: 5.2g, 3-pyridylboronic acid: 2.8g, Ginseng (dibenzylideneacetone)dipalladium (0): 0.4g, tricyclohexylphosphine: 0.5g, potassium carbonate: 3.9g, in 1,4-di

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, H ₂ O was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and purified with a monochlorobenzene solvent to obtain 2-(10-phenyl-anthracene-9-yl)-4,6-bis-{4-(pyridin-3-yl)-benzene White powder of yl}-pyrimidine (Compound-12): 1.5 g (yield 25%).

[化19]

The structure of the obtained white powder was identified by NMR.

The following 30 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=8.95(2H), 8.66(2H), 8.44(4H), 8.40(1H), 7.98(2H), 7.85(2H), 7.79(4H), 7.76(2H), 7.69-7.57(3H) ), 7.52(2H), 7.48-7.34(6H)

[Example 3]

<4,6-Bis-{4-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (Compound-19) >

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入H₂O，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結晶精製，獲得4,6-雙-{4-(吡啶-3-基)-苯基}-2-(9,9’-螺雙[9H]茀-2-基)-嘧啶(化合物-19)之白色粉體：3.0g(產率33%)。 Fill the reaction vessel with 4,6-bis-(4-chloro-phenyl)-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine: 8.0g, 3-pyridyl Boric acid: 3.8g, ginseng (dibenzylideneacetone) dipalladium (0): 0.6g, tricyclohexylphosphine: 0.7g, potassium carbonate: 5.4g, in 1,4-di

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, H ₂ O was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and refined with a monochlorobenzene solvent to obtain 4,6-bis-{4-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H ] White powder of 茀-2-yl)-pyrimidine (Compound-19): 3.0 g (yield 33%).

[化20]

The structure of the obtained white powder was identified by NMR.

The following 32 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=8.95(2H), 8.87(1H), 8.66(2H), 8.30(4H), 8.08(1H), 8.06(1H), 8.01-7.90(6H), 7.76(4H), 7.46-7.38 (5H), 7.17(2H), 7.14(1H), 6.83(2H), 6.75(1H)

[Example 4]

<2-(phenanthrene-2-yl)-4-{3-(pyridin-3-yl)-phenyl}-6-{4-(pyridin-3-yl)-phenyl}-pyrimidine (compound-27 ) Synthesis>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到2-(菲-2-基)-4-{3-(吡啶-3-基)-苯基}-6-{4-(吡啶-3-基)-苯基}-嘧啶(化合物-27)之白色粉體：6.0g(產率63%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-2-(phenanthrene-2-yl)-6-{3-(pyridin-3-yl)-phenyl}-pyrimidine: 8.9g, 3 -Pyridyl boronic acid: 2.3g, ginseng (dibenzylideneacetone) dipalladium (0): 0.5g, tricyclohexylphosphine: 1.0g, tripotassium phosphate: 7.3g, in 1,4-di

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 2-(phenanthrene-2-yl)-4-{3-(pyridine) White powder of -3-yl)-phenyl}-6-{4-(pyridin-3-yl)-phenyl}-pyrimidine (compound-27): 6.0 g (63% yield).

[化21]

The structure of the obtained white powder was identified by NMR.

The following 26 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.29(1H), 9.05(1H), 9.01(2H), 8.87(1H), 8.80(1H), 8.70(2H), 8.53(1H), 8.51(2H), 8.39(1H), 8.15(1H), 8.10-7.93(4H), 7.90-7.62(7H), 7.48(2H)

[Example 5]

<4-{3-(pyridin-3-yl)-phenyl}-6-{4-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀- Synthesis of 2-yl)-pyrimidine (Compound-31)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到4-{3-(吡啶-3-基)-苯基}-6-{4-(吡啶-3-基)-苯基}-2-(9,9'-螺雙[9H]茀-2-基)-嘧啶(化合物-31)之白色粉體：9.2g(產率76%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2 -Yl)-pyrimidine: 11.4g, 3-pyridylboronic acid: 2.3g, ginseng (dibenzylideneacetone)dipalladium (0): 0.5g, tricyclohexylphosphine: 0.5g, tripotassium phosphate: 7.4g, On 1,4-Tues

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 4-{3-(pyridin-3-yl)-phenyl}- 6-{4-(Pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (Compound-31) white powder: 9.2g (Yield 76%).

[化22]

The structure of the obtained white powder was identified by NMR.

The following 32 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=8.93(2H), 8.82(1H), 8.69(1H), 8.65(1H), 8.39(1H), 8.29(2H), 8.18(1H), 8.05(1H), 8.03(1H), 7.99(1H), 7.98-7.88(5H), 7.74(3H), 7.65(1H), 7.48-7.35(5H), 7.13(3H), 6.81(2H), 6.76(1H)

[Example 6]

<2-{4-(Naphthalene-1-yl)-phenyl}-4-{4-(pyridin-3-yl)-phenyl}-6-{4-(quinolin-8-yl)-benzene Synthesis of yl)-pyrimidine (Compound-36)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入甲醇，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結晶精製，獲得2-{4-(萘-1-基)-苯基}-4-{4-(吡啶-3-基)-苯基}-6-{4-(喹啉-8-基)-苯基}-嘧啶(化合物-36)之白色粉體：7.0g(產率74%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{4-(pyridin-3-yl)-phenyl}-2-{4-(naphthalene-1-yl)-phenyl} -Pyrimidine: 8.0g, 8-quinolinylboronic acid: 2.8g, ginseng (dibenzylideneacetone) dipalladium (0): 0.4g, tricyclohexylphosphine: 0.4g, tripotassium phosphate: 6.2g, in 1 ,4-two

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and refined with a monochlorobenzene solvent to obtain 2-{4-(naphthalene-1-yl)-phenyl}-4-{4-(pyridin-3-yl)-phenyl} White powder of 6-{4-(quinolin-8-yl)-phenyl}-pyrimidine (Compound-36): 7.0 g (yield 74%).

[化23]

The structure of the obtained white powder was identified by NMR.

The following 30 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.03(1H), 9.00(1H), 8.93(2H), 8.69(1H), 8.51(4H), 8.29(1H), 8.20(1H), 8.09-7.78(10H), 7.74(2H) ), 7.70(1H), 7.65-7.41(6H)

[Example 7]

<4,6-Bis-{4-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (Compound-84) >

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入H₂O，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結晶精製，獲得4,6-雙-{4-(吡啶-3-基)-苯基}-2-(9,9'-螺雙[9H]茀-2-基)-嘧啶(化合物-84)之白色粉體：2.6g(產率28%)。 Fill the reaction vessel with 4,6-bis-(4-chloro-phenyl)-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine: 8.2g, 3-pyridyl Boric acid: 3.9g, ginseng (dibenzylideneacetone) dipalladium (0): 0.6g, tricyclohexylphosphine: 0.7g, potassium carbonate: 5.5g, in 1,4-di

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, H ₂ O was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and refined with a monochlorobenzene solvent to obtain 4,6-bis-{4-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H ] White powder of 茀-2-yl)-pyrimidine (Compound-84): 2.6 g (yield 28%).

[化24]

The structure of the obtained white powder was identified by NMR.

The following 32 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=8.97(2H), 8.66(2H), 8.49(4H), 8.34(1H), 7.99(2H), 7.88(3H), 7.82(4H), 7.79(1H), 7.43(4H), 7.39(1H), 7.16(2H), 7.10(2H), 6.90(2H), 6.87(1H), 6.76(1H)

[Example 8]

<4,6-Bis-{4-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-3-yl)-pyrimidine (Compound-85) >

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到4,6-雙-{4-(吡啶-3-基)-苯基}-2-(9,9’-螺雙[9H]茀-3-基)-嘧啶(化合物-85)之白色粉體：2.6g(產率28%)。 Fill the reaction vessel with 4,6-bis-(4-chloro-phenyl)-2-(9,9'-spirobis[9H]茀-3-yl)-pyrimidine: 7.0g, 3-pyridyl Boric acid: 3.3g, ginseng (dibenzylideneacetone) dipalladium (0): 0.3g, tricyclohexylphosphine: 0.3g, tripotassium phosphate: 4.8g, in 1,4-di

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 4,6-bis-{4-(pyridin-3-yl)- White powder of phenyl}-2-(9,9'-spirobis[9H]茀-3-yl)-pyrimidine (Compound-85): 2.6 g (yield 28%).

[化25]

The structure of the obtained white powder was identified by NMR.

The following 34 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.11(1H), 9.00(2H), 8.70(2H), 8.68(1H), 8.48(4H), 8.17(1H), 8.03(3H), 7.85(4H), 7.62(1H), 7.47(4H), 7.38-7.21(11H)

[Example 9]

<4-{4-(isoquinolin-4-yl)-phenyl}-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H] Synthesis of pyrimidine-2-yl)-pyrimidine (compound-86)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到4-{4-(異喹啉-4-基)-苯基}-6-{3-(吡啶-3-基)-苯基}-2-(9,9'-螺雙[9H]茀-2-基)-嘧啶(化合物-86)之白色粉體：8.1g(產率63%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2 -Yl)-pyrimidine: 11.3g, 4-isoquinolinylboronic acid: 3.6g, ginseng (dibenzylideneacetone)dipalladium (0): 0.5g, tricyclohexylphosphine: 0.5g, tripotassium phosphate: 7.3 g, at 1,4-Tues

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 4-{4-(isoquinolin-4-yl)-phenyl }-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (compound-86) white powder: 8.1g (63% yield).

[化26]

The structure of the obtained white powder was identified by NMR.

The following 34 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.30(1H), 8.93(1H), 8.84(1H), 8.69(1H), 8.54(1H), 8.40(1H), 8.33(2H), 8.19(1H), 8.06(4H), 7.95(2H), 7.92(2H), 7.89(1H), 7.77-7.60(6H), 7.45(1H), 7.41(2H), 7.37(1H), 7.14(3H), 6.81(2H), 6.75(1H) )

[Example 10]

<4-{3-(Pyridin-3-yl)-phenyl}-6-{4-(quinolin-8-yl)-phenyl}-2-(9,9'-spirobis[9H]茀Synthesis of -2-yl)-pyrimidine (Compound-87)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到4-{3-(吡啶-3-基)-苯基}-6-{4-(喹啉-8-基)-苯基}-2-(9,9'-螺雙[9H]茀-2-基)-嘧啶(化合物-87)之白色粉體：4.0g(產率50%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2 -Yl)-pyrimidine: 7.0g, 8-quinolinylboronic acid: 2.2g, ginseng (dibenzylideneacetone) dipalladium (0): 0.3g, tricyclohexylphosphine: 0.1g, tripotassium phosphate: 4.5g , On 1,4-Tues

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 4-{3-(pyridin-3-yl)-phenyl}- 6-{4-(quinolin-8-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (compound-87) white powder: 4.0 g (50% yield).

[化27]

The structure of the obtained white powder was identified by NMR.

The following 34 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.00(1H), 8.93(1H), 8.84(1H), 8.69(1H), 8.36(1H), 8.29(2H), 8.24(1H), 8.16(1H), 8.06(1H), 8.03(1H), 8.02(1H), 7.96-7.82(7H), 7.79(1H), 7.73(1H), 7.65(1H), 7.62(1H), 7.46(1H), 7.43(1H), 7.38(3H) ), 7.13(3H), 6.81(2H), 6.76(1H)

[Example 11]

<4-{3-(Pyridin-3-yl)-phenyl}-6-{4-(quinolin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀Synthesis of -2-yl)-pyrimidine (Compound-88)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到4-{3-(吡啶-3-基)-苯基}-6-{4-(喹啉-3-基)-苯基}-2-(9,9'-螺雙[9H]茀-2-基)-嘧啶(化合物-88)之白色粉體：5.2g(產率60%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2 -Yl)-pyrimidine: 7.0g, 3-quinolinyl borate: 3.3g, ginseng (dibenzylideneacetone)dipalladium (0): 0.3g, tricyclohexylphosphine: 0.1g, tripotassium phosphate: 4.5g in 1,4-two

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 4-{3-(pyridin-3-yl)-phenyl}- 6-{4-(quinolin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (compound-88) white powder: 5.2 g (60% yield).

[化28]

The structure of the obtained white powder was identified by NMR.

The following 34 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.27(1H), 8.96(1H), 8.86(1H), 8.72(1H), 8.41(2H), 8.36(2H), 8.22(1H), 8.19(1H), 8.08(1H), 8.07(1H), 8.04(1H), 7.99-7.86(7H), 7.79(1H), 7.76(1H), 7.67(2H), 7.48(1H), 7.45(1H), 7.41(2H), 7.16(3H) ), 6.84(2H), 6.78(1H)

[Example 12]

<4-{3-(pyridin-3-yl)-phenyl}-6-{4-(pyridin-4-yl)-phenyl}-2-(9,9'-spirobis[9H]茀- Synthesis of 2-yl)-pyrimidine (Compound-89)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，藉分液操作對有機層進行分液萃取及減壓下濃縮。將所得粗製生成物藉由管柱層析法(載體：矽膠，洗提液：二氯甲烷/醋酸乙酯)進行精製，得到4-{3-(吡啶-3-基)-苯基}-6-{4-(吡啶-4-基)-苯基}-2-(9,9'-螺雙[9H]茀-2-基)-嘧啶(化合物-89)之白色粉體：6.4g(產率85%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{3-(pyridin-3-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2 -Yl)-pyrimidine: 7.0g, 4-pyridylboronic acid: 1.4g, ginseng (dibenzylideneacetone)dipalladium (0): 0.3g, tricyclohexylphosphine: 0.1g, tripotassium phosphate: 4.5g, On 1,4-Tues

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, the organic layer was separated and extracted and concentrated under reduced pressure by liquid separation operation. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate) to obtain 4-{3-(pyridin-3-yl)-phenyl}- 6-{4-(pyridin-4-yl)-phenyl}-2-(9,9'-spirobis[9H]茀-2-yl)-pyrimidine (compound-89) white powder: 6.4g (The yield is 85%).

[化29]

The structure of the obtained white powder was identified by NMR.

The following 32 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=8.95(1H), 8.84(1H), 8.73(3H), 8.40(1H), 8.31(2H), 8.19(1H), 8.07(1H), 8.05(1H), 8.01(1H), 7.99-7.91(4H), 7.81(2H), 7.76(1H), 7.66(1H), 7.59(2H), 7.49-7.37(4H), 7.16(3H), 6.83(2H), 6.78(1H)

[Example 13]

<2-{4-(Naphthalene-1-yl)-phenyl}-4-{4-(pyridin-3-yl)-phenyl}-6-{4-(quinolin-3-yl)-benzene Synthesis of yl)-pyrimidine (Compound-93)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入甲醇，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結晶精製，獲得2-{4-(萘-1-基)-苯基}-4-{4-(吡啶-3-基)-苯基}-6-{4-(喹啉-3-基)-苯基}-嘧啶(化合物-93)之白色粉體：4.8g(產率51%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{4-(pyridin-3-yl)-phenyl}-2-{4-(naphthalene-1-yl)-phenyl} -Pyrimidine: 8.0g, 3-quinolinyl borate: 4.1g, ginseng (dibenzylideneacetone) dipalladium (0): 0.4g, tricyclohexylphosphine: 0.4g, potassium carbonate: 6.2g, 1,4-Tues

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and refined with a monochlorobenzene solvent to obtain 2-{4-(naphthalene-1-yl)-phenyl}-4-{4-(pyridin-3-yl)-phenyl} -White powder of 6-{4-(quinolin-3-yl)-phenyl}-pyrimidine (Compound-93): 4.8 g (yield 51%).

[化30]

The structure of the obtained white powder was identified by NMR.

The following 30 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.31(1H), 8.99(1H), 8.91(2H), 8.68(1H), 8.51(4H), 8.42(1H), 8.20(1H), 8.16(1H), 8.08-7.88(7H) ), 7.83(2H), 7.79(1H), 7.74(2H), 7.68-7.39(6H)

[Example 14]

<4-{4-(isoquinolin-4-yl)-phenyl}-2-{4-(naphthalene-1-yl)-phenyl}-6-{4-(pyridin-3-yl)- Synthesis of phenyl}-pyrimidine (Compound-94)>

烷、H₂O混合溶劑下進行迴流攪拌一晚。放冷後，於系統內加入甲醇，將析出之固體過濾獲得粗製生成物。將所得粗製生成物藉由單氯苯溶媒進行再結晶精製，獲得4-{4-(異喹啉-4-基)-苯基}-2-{4-(萘-1-基)-苯基}-6-{4-(吡啶-3-基)-苯基}-嘧啶(化合物-94)之白色粉體：5.1g(產率54%)。 Fill the reaction vessel with 4-(4-chloro-phenyl)-6-{4-(pyridin-3-yl)-phenyl}-2-{4-(naphthalene-1-yl)-phenyl} -Pyrimidine: 8.0g, 4-isoquinolinylboronic acid: 2.8g, ginseng (dibenzylideneacetone) dipalladium (0): 0.4g, tricyclohexylphosphine: 0.4g, potassium carbonate: 6.2g, in 1 ,4-two

Reflux and stir overnight in a mixed solvent of alkane and H ₂ O. After cooling, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The obtained crude product was recrystallized and purified with a monochlorobenzene solvent to obtain 4-{4-(isoquinolin-4-yl)-phenyl}-2-{4-(naphthalene-1-yl)-benzene White powder of yl}-6-{4-(pyridin-3-yl)-phenyl}-pyrimidine (Compound-94): 5.1 g (54% yield).

[化31]

The structure of the obtained white powder was identified by NMR.

The following 30 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).

δ(ppm)=9.35(1H), 9.01(1H), 8.93(2H), 8.69(1H), 8.62(1H), 8.54(4H), 8.22(1H), 8.12(1H), 8.03(2H), 7.95(2H), 7.86(2H), 7.80(2H), 7.75(2H), 7.70(2H), 7.65-7.42(6H)

[Example 15]

For the pyrimidine compound represented by general formula (1), the melting point and glass transition point were measured by a high-sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100SA). The results are shown in Table 1. In addition, "─" indicates that the melting point-based vapor deposition index cannot be observed due to the high amorphous nature, and the glass transition point (Tg) is an index of the stability of the film state.

[Table 1]

The compound having a pyrimidine ring structure represented by the general formula (1) has a glass transition point above 98°C, indicating a stable film state.

[Example 16]

Using a compound having a pyrimidine ring structure represented by the general formula (1), a vapor-deposited film with a thickness of 100 nm was formed on an ITO substrate, and measured by an ionization potential measuring device (manufactured by Sumitomo Heavy Industries Co., Ltd., PYS-202) Work function. The results are shown in Table 2. The work function is an indicator of the hole transportability or the hole resistance.

[Table 2]

The compound with a pyrimidine ring structure represented by the general formula (1) has a value greater than 5.5 eV of the work function of general hole transport materials such as NPD and TPD, and has a larger hole blocking ability.

[Example 17]

The organic EL element is shown in Figure 1. On a glass substrate 1 that is preformed with an ITO electrode as a transparent anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a The hole blocking layer 6, the electron transport layer 7, the electron injection layer 8, and the cathode (aluminum electrode) 9 are produced.

Specifically, the glass substrate 1 on which ITO with a film thickness of 50 nm was formed was ultrasonically cleaned in isopropanol for 20 minutes, and then dried on a hot plate heated to 200° C. for 10 minutes. Then, after 15 minutes of UV ozone treatment, the glass substrate with ITO was installed in a vacuum vapor deposition machine, and the pressure was reduced to 0.001 Pa or less. Next, as the hole injection layer 3 covering the transparent anode 2, the electron acceptor (Acceptor-1) of the following structural formula and the compound (HTM-1) of the following structural formula are formed according to the vapor deposition rate ratio Acceptor-1: Compound (HTM-1)=3: 97. Binary vapor deposition is performed to form a hole injection layer 3 with a thickness of 10 nm. On this hole injection layer 3, a compound (HTM-1) of the following structural formula was formed into a film thickness of 60 nm as the hole transport layer 4. On the hole transport layer 4, as the light-emitting layer 5, the compound EMD-1 of the following structural formula and the compound EMH-1 of the following structural formula are made EMD-1 at the vapor deposition rate ratio: EMH-1=5 : A vapor deposition rate of 95 performs binary vapor deposition to form a light-emitting layer 5 with a film thickness of 20 nm. On the light-emitting layer 5, the compound of Example 1 of the present invention (compound-5) and the compound (ETM-1) of the following structural formula are converted into compound-5 according to the vapor deposition rate ratio: ETM-1=50:50 The vapor deposition rate is binary vapor deposition to form a hole blocking layer and electron transport layer 6 and 7 with a film thickness of 30 nm. On this hole blocking layer and electron transport layer 6 and 7, lithium fluoride was formed to have a thickness of 1 nm as the electron injection layer 8. Finally, aluminum was vapor-deposited for 100 nm to form the cathode 9. The properties of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the measurement results of the luminescence characteristics of the produced organic EL device when a DC voltage is applied.

[化32]

[化33]

[化34]

[Example 18]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 2 (Compound-12) was used and evaporated The deposition rate ratio was compound-12: ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 19]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 3 (Compound-19) was used and evaporated The deposition rate ratio was compound -19: ETM-1 = 50: 50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 20]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 4 (Compound-27) was used and evaporated The deposition rate ratio is compound-27: ETM-1 = 50: 50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 21]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 5 (Compound-31) was used and evaporated The deposition rate ratio was compound-31:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 22]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 6 (Compound-36) was used and evaporated The deposition rate ratio was compound-36:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 23]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 7 (Compound-84) was used and evaporated The deposition rate ratio was compound-84:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 24]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 8 (Compound-85) was used and evaporated The deposition rate ratio was compound-85:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 25]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 9 (Compound-86) was used and evaporated The deposition rate ratio was compound-86:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 26]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole blocking layer and electron transport layer 6 and 7, the compound of Example 10 (Compound-87) was used and evaporated The deposition rate ratio was compound-87:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 27]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 11 (Compound-88) was used and evaporated The deposition rate ratio was compound-88:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 28]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 12 (Compound-89) was used and evaporated The deposition rate ratio was compound-89:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 29]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 13 (Compound-93) was used and evaporated The deposition rate ratio was compound-93:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Example 30]

In Example 17, in addition to substituting the compound of Example 1 (Compound-5) of the present invention as the material of the hole stop layer and electron transport layer 6 and 7, the compound of Example 14 (Compound-94) was used and evaporated The deposition rate ratio was compound-94:ETM-1=50:50. Except for binary vapor deposition, the organic EL device was produced under the same conditions. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[Comparative Example 1]

For comparison, in Example 17, in addition to substituting the compound of Example 1 of the present invention (Compound-5) as the material of the hole stop layer and electron transport layer 6 and 7, the compound of the following structural formula (ETM-2) was used (For example, refer to Patent Document 6), and the organic EL element was produced under the same conditions except for performing binary vapor deposition at a vapor deposition rate of ETM-2:ETM-1=50:50. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[化35]

[Comparative Example 2]

For comparison, in Example 17, in addition to substituting the compound of Example 1 of the present invention (Compound-5) as the material of the hole stop layer and electron transport layer 6 and 7, the compound of the following structural formula (ETM-3) was used (For example, refer to Patent Document 8), and the organic EL device was produced under the same conditions except for performing binary vapor deposition at a vapor deposition rate ratio of ETM-3:ETM-1=50:50. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[化36]

[Comparative Example 3]

For comparison, in Example 17, in addition to substituting the compound of Example 1 of the present invention (Compound-5) as the material of the hole blocking layer and electron transport layer 6 and 7, the compound of the following structural formula (ETM-4) was used (For example, refer to Patent Document 9), and the organic EL element was produced under the same conditions except for performing binary vapor deposition at a vapor deposition rate ratio of ETM-4:ETM-1=50:50. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[化37]

[Comparative Example 4]

For comparison, in Example 17, in addition to substituting the compound of Example 1 of the present invention (Compound-5) as the material of the hole stop layer and electron transport layer 6 and 7, the compound of the following structural formula (ETM-5) was used (For example, refer to Patent Document 10), the organic EL element was produced under the same conditions except for performing binary vapor deposition at a vapor deposition rate ratio of ETM-5: ETM-1=50:50. The characteristics of the produced organic EL device were measured in the air and at room temperature. Table 3 shows the results of the measurement of the luminescence characteristics when a DC voltage is applied to the organic EL elements produced.

[化38]

The device life was measured using the organic EL devices produced in Example 17 to Example 30 and Comparative Example 1 to Comparative Example 4. The results are shown in Table 3 together. The life of the device is to set the luminous brightness at the start of light emission (initial brightness) to 2000cd/m ² for constant current drive, and measure the luminous brightness attenuation to 1900cd/m ² (equivalent to 95% when the initial brightness is set to 100%: 95% attenuation).

table 3

As shown in Table 1, the driving voltage when the current density is 10mA/cm ² is relative to 3.72~4.01V of the organic EL device of Comparative Example 1 to Comparative Example 4. The organic EL device of Example 17 to Example 30 The low voltage in the EL element is 3.31~3.59V.

In terms of luminous efficiency, compared to the 6.59~8.05 cd/A of the organic EL device of Comparative Example 1 to Comparative Example 4, the organic EL device of Example 17 to Example 30 is improved to 8.21~8.99 cd/A.

In terms of power efficiency, compared to the 5.16~6.62 lm/W of the organic EL devices of Comparative Examples 1 to 4, the organic EL devices of Examples 17 to 30 are greatly improved to 7.38~8.32 lm/W.

In terms of device life (95% attenuation), compared to the 165~203 hours of the organic EL device of Comparative Example 1 to Comparative Example 4, the organic EL device of Example 17 to Example 30 has a significantly longer life to 239~293 hours .

In this way, the organic EL device of the present invention is an organic EL device having excellent luminous efficiency and power efficiency, and a long life.

(Industrial availability)

The compound with a pyrimidine ring structure of the present invention has good electron injection characteristics, excellent hole blocking ability, and is stable in a thin film state, so it is suitable as a compound for organic EL devices. By using the compound to produce an organic EL element, high efficiency can be obtained, driving voltage can be reduced, and durability can be improved. It can be developed for applications such as household electrical products or lighting.

Claims (14)

A compound with a pyrimidine ring structure, represented by the following general formula (a-1); [化1]

(In the formula, A and B may be the same or different from each other, and represent the following structural formula (b-1); Ar represents substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group; R represents hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic ring Groups, substituted or unsubstituted condensed polycyclic aromatic groups, linear or branched alkyl groups with 1 to 6 carbon atoms that may have substituents, and 5-10 carbon atoms that may also have substituents The cycloalkyl group, the linear or branched alkenyl group with 2 to 6 carbon atoms, and the linear or branched chain with 1 to 6 carbon atoms that may also have a substituent Alkyloxy group or cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent;) [化2] ----L──Het (b-1) (In the formula, L represents a divalent group of a single bond, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; Het represents substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted three

Group, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted indolyl, substituted or unsubstituted azepinyl, substituted Or unsubstituted diazaspirodiazepine group, substituted or unsubstituted azaspirodiazepine group, or substituted or unsubstituted diazaspirodiazepine group, the dotted line indicates the bonding site with the pyrimidine ring). For example, the compound having a pyrimidine ring structure in claim 1 is represented by the following general formula (a-2); [化3]

(In the formula, A, B, Ar and R have the same meaning as the general formula (a-1) above). The compound having a pyrimidine ring structure in claim 1 is represented by the following general formula (a-3); [化4]

(In the formula, A, B, Ar and R have the same meaning as the general formula (a-1) above). The compound having a pyrimidine ring structure according to claim 2, wherein A and B are different from each other. The compound having a pyrimidine ring structure according to claim 3, wherein A and B are different from each other. The compound having a pyrimidine ring structure according to claim 4, wherein L in the above structural formula (b-1) represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted Substituted anthracenyl, substituted or unsubstituted phenanthrenyl, or substituted or unsubstituted biphenyl. The compound having a pyrimidine ring structure according to claim 5, wherein L in the above structural formula (b-1) represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted Substituted anthracenyl, substituted or unsubstituted phenanthrenyl, or substituted or unsubstituted biphenyl. The compound having a pyrimidine ring structure according to claim 6, wherein Het in the above structural formula (b-1) represents unsubstituted pyridyl, unsubstituted quinolinyl, unsubstituted isoquinolinyl, or unsubstituted The phenanthroline. The compound having a pyrimidine ring structure according to claim 7, wherein Het in the above structural formula (b-1) represents an unsubstituted pyridyl group, an unsubstituted quinolyl group, an unsubstituted isoquinolyl group, or an unsubstituted The phenanthroline. An organic electroluminescence element having a pair of electrodes and at least one organic layer sandwiched between them; characterized in that the compound having a pyrimidine ring structure described in any one of claims 1 to 9 is used as The constituent material of at least one organic layer. The organic electroluminescent device of claim 10, wherein the above-mentioned use has pyrimidine The organic layer of the ring structure compound is the electron transport layer. The organic electroluminescence device of claim 10, wherein the organic layer using the compound having a pyrimidine ring structure is a hole blocking layer. The organic electroluminescence device according to claim 10, wherein the organic layer using the compound having a pyrimidine ring structure is a light-emitting layer. The organic electroluminescence device according to claim 10, wherein the organic layer using the compound having a pyrimidine ring structure is an electron injection layer.

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